JPS609080B2 - Liquid enzyme-containing detergent composition - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to liquid, homogeneous, substantially builder-free, enzyme-containing detergent compositions.

PRIOR ART Severely soiled knitted fabrics (Fabric).

The liquid detergent composition must contain a sufficient concentration of the detergent composition for cleaning or pre-treating and then cleaning textiles, in particular cotton and synthetic textiles (hereinafter referred to as "textiles").
Liquid detergent compositions must be stable and uniform under a variety of storage conditions, and can be used in both horizontal (rotating drum) and upright (vertical traversal) washing machines; Topical application as well as hand washing should be done appropriately. Synthetic organic detergent compounds (generally aeon type, nonionic type, or mixed anionic-nonionic type)
Liquid, heavy-duty detergent compositions containing an inorganic builder type, an inorganic builder type, and a solvent are described, for example, in U.S. Pat. No. 25,516.
No. 34, No. 1908651, No. 2920045, No. 2947702, No. 3239468, No. 32727
No. 53, No. 3393154, No. 3554916, No. 3697451, No. 3709838, Belgian Patent No. 613165, No. 665532, No. 794713
British Patent No. 759877, British Patent No. 842813, and German Patent No. 161711
No. 9, No. 1937682, No. 2327861, No. 2
No. 53084, No. 2361448 and No. 2362
No. 114 each specification.

These compositions now contain hydrotropes or solubilizers to allow addition of sufficient amounts of surfactants and conventional builder salts to obtain a suitable working volume/performance ratio. There is. Still other compositions are substantially anhydrous liquid compositions containing an alkanolamine component (US Pat. No. 3,528,925). Still other compositions contain soap ingredients (US Pat. Nos. 2,875,153 and 2,543,744). It is well known that formulating enzyme-containing liquid detergent compositions is a very delicate task because the enzyme activity in liquid soot rapidly decreases during storage. In fact, the various problems caused by the irreversible loss of enzyme activity are of a type that to this day cannot be satisfactorily solved. The importance of such obstacles is even better understood when one considers that it is already highly desirable to formulate liquid detergent compositions containing enzymes. The lack of a practical solution to this highly unsatisfactory retention of enzyme activity in aqueous detergent soots demonstrates the instability of enzymes in currently commercially available liquid detergent compositions and the market value. This also confirms the difficulty in selectively blending certain enzyme-containing liquid compositions. Regarding this field of detergent technology, there is a fragmentation of the state of the art.

For example, it is known from Dutch Patent Application No. 6,608,106 that proteolytic enzymes have only limited stability in aqueous media.

In addition to this, most detergent ingredients such as phosphates, carbonates and sulfates have been described to have an adverse effect on the activity of such enzymes as well as their stability in detergent solutions. The above-mentioned Dutch patent ends in explaining why proteolytic enzymes are to date only included in granular detergent compositions. However, no concrete solution to the lack of stability has been shown to those skilled in the art. ``The power of biochemistry.
workman. Biofiji power. Acta” (BLOCHEMICA)
ET BIOPHYSICA ACTA), Volume 6 (1
950), as is known from the explanation below,
Sequestering agents generally have a destabilizing effect on proteolytic enzymes in aqueous soot. citric acid, oxalic acid,
Ethylenediaminetetraacetic acid and nitrilotriacetic acid provide examples of such known destabilizing effects. German Patent Application DOS No. 2301728 is representative of the known art. It is stated therein that various enzyme preparations can be included in liquid detergent compositions, preferably in combination with detergent sequestrant builders.
As can be seen from the foregoing, significant efforts have been made to develop liquid builder-containing and builder-free detergent compositions.

However, hitherto known compositions are unsuitable for large-scale use, undesirable from an ecological point of view in untreated sewage, and problematic from a performance point of view in the cleaning of natural and synthetic fibers. In addition, there are a few other problems, such as inactivation of enzyme components during storage. It has been discovered that these known drawbacks can be prevented by formulating enzyme-containing liquid detergent compositions containing small amounts of polyacids and certain levels of free calcium ions.

It also contains a mixture of major amounts of polyexylated nonionic surfactants and synthetic anionic surfactants in combination with polyacids, proteases and free calcium ions, p
Liquid, concentrated, heavy-duty detergent compositions with H in the range of 6.0 to 7.5 can be used to remove bleach-sensitive detergents by topical application and by washing fabrics.
e) It has been discovered that it exhibits an excellent dirt removal effect.

Liquid concentrated heavy-duty detergent compositions of this type exhibit excellent physical properties, are homogeneously stable under harsh storage conditions, and withstand many conventional additions. It is an object of the present invention to provide a liquid, concentrated, homogeneous, stable, enzyme-containing, heavy-duty detergent composition that exhibits excellent cleaning power and excellent bleach-sensitive stain removal upon topical application and fabric washing. It is about providing something.

Another object of the invention is to provide a liquid, concentrated, homogeneous, stable, heavy-duty detergent composition that retains effective enzymatic activity under long-term storage conditions.

Yet another object of the present invention is to provide a liquid, concentrated, homogeneous, stable, enzyme-containing heavy duty detergent composition that is ecologically acceptable.

These and other objects will become apparent from the description below.

Summary of the Invention The liquid composition of the present invention contains the following 'a} to (e}.

{a} A mixture comprising from about 35% to about 75% (by weight) of an ethoxylated nonionic surfactant and a synthetic anionic surfactant.

However, the weight ratio of nonionic surfactant to anionic surfactant is from about 1:1 to about 5:1. {b} 0.05
% to about 1.5% (by weight) of water-soluble Ca rust compounds (co
polyacids that can form complexes.

{c} 0.5 mmol/liter to 15 mmol/liter free calcium ion. 'd} 0.001%
~2% of an alkaline proteolytic enzyme with an isodew point greater than about 8.

{e} A liquid carrier comprising water and about 2% to about 15% (by weight) of the total composition of a lower aliphatic alcohol.

However, the pH of this composition is about 6.0 to about 7.5.
In a preferred embodiment, the polyacid is between 0.05% and 1
．． 0% (by weight), in which case the polyacid is present in a range of 0.3-0.6% (by weight), preferably 0.5% (by weight).
Enzyme stability comparable to that obtained by adding citric acid (by weight) can be produced. The stability in the case of this polyacid and citric acid is determined for the same composition of the invention. The logarithm of the stability constant of the Ca-Tsuba compound of the polyacid is greater than 1.5 in the composition matrix,
More preferably, it is in the range of 2.0 to 4.0. As used herein, "free calcium ion" or "
The term "calcium ion" shall mean calcium that is not bound by a polyacid (sequestering agent).

DETAILED DESCRIPTION OF THE INVENTION These essential components will be explained in more detail below.

Unless otherwise specified, percentages are by weight.

Ethoxylated Nonionic Surfactants Ethoxylated nonionic surfactants can be represented by all detergent ethosylates known to be useful in detergent technology.

Such nonionic compounds condense ethylene oxide with hydrocarbons having reactive hydrogen atoms, such as hydroxyl, carboxyl, or amino groups, to form hydrophilic moieties, i.e., ethenoxy chains; Conveniently, they are prepared by forming hydrophobic moieties in the presence of a catalyst.Such a process results in product mixtures containing a number of non-ionic compounds in varying amounts of ethoxylates. "General formula R-A (C
H2CH20) mH (in this formula R represents a hydrophobic moiety and A represents a group having a reactive hydrogen atom), the usual designation "m" for the ethylene oxide units present per molecule of a nonionic compound; is an expression of the average number of ethylene oxide units per nonionic compound molecule according to a statistical distribution centered on this "m" number. The properties of ethoxylated nonionic surfactants "depend to a large extent on the average number of hydrophilic moieties, ie ethylene oxide units, present therein.

Most commercially available polyethoxylated nonionic compounds are viscous liquids or soft pastes, generally having an average of about 2 to 24 ethylene oxide units. The ethoxylated nonionic detergent compounds that can be used in the compositions of the invention are obtained by reacting alcohol with ethylene oxide and are soluble in the liquid compositions of the invention. Ethoxylated nonionic compounds have a negative temperature coefficient of solubility in water, and the higher the temperature, the more insoluble they become.

Therefore, soluble in the liquid composition of the present invention means about 35
It means that it is soluble at a temperature below 0.00. Typically, ethoxylated nonionic surfactants are considered to include only water-soluble compounds.

There are many ethoxyl nonionic compounds that have cleaning properties but are not hydrophilic enough to be sufficiently water soluble and are dispersed in water. However, these compounds can be made water columnar by mixing with highly soluble ethoxylated nonionic compounds using solubilizing agents such as lower aliphatic alcohols, or by hydrotroping. However, soluble in the liquid composition of the present invention means that it is water-soluble per se, or that it is soluble in the liquid composition of the present invention,
means. The hydrophobic moiety of the nonionic compound used in the compositions of the invention can be straight chain or branched, saturated or uncontained, having from about 8 to about 24, preferably from about 12 to 2, solid carbon atoms. It can be derived from saturated primary and secondary aliphatic alcohols. Other sources include the alkyl group(s) having from 1 to about 12 carbon atoms, at least one alkyl group having at least 6 carbon atoms, and the carbon atoms in the alkyl group having at least 6 carbon atoms. Maximum total number is about 13
It is a hard alkylphenol. Primary alcohols can be derived, for example, from animal oils, vegetable oils, fats or the corresponding fatty acids by hydrogenolysis.

The primary alcohol is a substantially straight chain or linear alcohol. Primary alcohols can also be obtained from synthetic raw materials by various processes. Typical raw materials are lower alkylene or olefin polymers. Depending on the type of polymer, olefin, process and process conditions, alcohols with varying linear or branched character can be obtained. Most of the commercially available primary synthetic alcohols are manufactured using the “OXO” method or “
made by either the Ziegler method. Secondary alcohols are produced from synthetic raw materials, such as olefins, by direct hydration at high temperatures and pressures or by hydrolysis of intermediate sulfuric acid products.
It can also be obtained by a paraffin oxidation method. Alkylphenols are obtained by reaction with olefins thermally, preferably in the presence of a catalyst such as boron trifluoride.

Also, xylenol and cresol can be used in place of phenol. For the compositions of the invention, polyethoxylated nonionic compounds derived from primary and secondary aliphatic alcohols are preferred.

The hydrophilic portion of the nonionic compound used in the compositions of the invention is an ethenoxy chain consisting of an average of 2 to about 24 ethylene oxide units depending on the hydrophobicity of the hydrocarbon group.

Ethenoxy chains containing at least about 4 ethylene oxide units are preferred. Suitable examples of ethoxylated nonionic surfactants include, for example, aliphatic primary alcohols having from 12 to 2 carbon atoms in amounts ranging from about 4 moles to about 4 moles per mole of alcohol.
It can be made by condensation with about 14 moles of ethylene oxide. Non-limiting examples of ethoxylated nonionic surfactants derived from straight chain primary aliphatic alcohols are as follows. C, 2nd day customer 10-
(C2 day 0) 3 days, C, 6 & 3-○- (C2 day 0) 9
-day, C, 8th day 851○-(C2 day 40) 9-day, C,
8th 37-○- (C2th 40) 9th, C, 4th 29-
○-(C2 days 0) 9-days, C, 2 days 25-days, ○-(C2 days 40) 9-days, CI 2 days 25-days.

One (C2 days 4) 4 days, CI 5 days 33 one. -(C2 ratio○
) 9 days, tallow alkyl ○- (C2 ratio ○),. one day,
C,. Day 23-○1 (C2 ratio○) 4 days, C, 5 days 33
-○- (C2 days○)7-days, and mixtures thereof. Non-limiting examples of ethoxylated nonionic surfactants derived from secondary aliphatic alcohols include: CI 2nd day 25CH (C4th day 9)-.

- (C2 day 40) 9-day, C8 day 17CH (C4 day 9)
−. 1 (C2 days 40) 12 days, (C7 days, 5) 2CH
-○- (C2 is ○) 6 days, C, 7 ratio 5CH (CH3)
-○- (C2 days 40) 9 days, C,4 ratio 9CH (C3 days 7)-. 1 (C2 days 40) 9 days, CI 4 days 29CH (
C ratio) -○- (C2 day 0) 9 days, and mixtures thereof. Non-limiting examples of ethoxylated nonionic surfactants derived from branched primary aliphatic alcohols include:

C.I.

H phantom CH (CH3) CH2-1. 1 (C2 day 40) 9-day, CI 2nd day doctor CH (CH3) CH2-.・(C2 day 40
)11-day, C,5 is CH(CH3)CH2101(
C2 days 40) 9 days, C,3 ratio? CH(CH3)C Uniform CH2-C Uniform ○-(C2 days ○) 9 days C, 2 days cloudy C
H (C2 days 5) - CQ - ○ - (C2 days 40) 9 days, (
C7 day, 5) 2CH-C ratio -○- (C2 day ○), 2-day "C9 day, 9CH (C8 day, 7) CH2-0 one (C2
Day 40), 2nd day, C, 3rd day illusion CH (C4 day 9) C criticism 101 (C2 is ○), . 1 day, C, 3 days 27CH-(C3
day 7) CH2-C ratio 1○- (C2 day 40) 9-day, and mixtures thereof. Non-limiting examples of ethoxylated nonionic surfactants derived from alkylphenols include:

C9 days, 9C6 ratio 1○-(C2 days 40)9-days, C,2
Day 25C6 day 41 ○- (C2 ratio ○), 2 day, (C9 day, 9) (CH3) C6 day 3-.

- (C2 days 40) 12-days, (CI2 days cloudy) (CH3)
2C6 day 21. - (C2 days 40) 11-days, CI2 days 2
5C6 days 14-. - (C2 ratio ○) 6 days, and mixtures thereof. Non-limiting examples of mixtures of ethoxylated nonionic surfactants comprising weakly water-soluble and highly water-soluble nonionic compounds that can be used in the compositions of the invention include: . C, 2 day cloudiness -○-(C
2 ratio ○) 5 days and C, 2 days 25-○- (C2 ratio 0), 2
-day 1/2 mixture, C,4Q9-○-(C2 ratio○)5
-Day and tallow alkyl-○-(C2 ratio○),. 1/ of the day
1 mixture, C, 5 days 3, 1○- (C2 days 40) 7-days and tallow alkyl-○- (C2 mountains 0), . 2/1 mixture per day, C, oH milk-○ (C2 days 40) 3-days and C, 3 days 2
7CH(CH3)CH2-0-(C2 day 40),. 1/4 mixture of the day, C8 day, 7CH (C6 day, 3) -○-
(C2 ○) 6 days and C. 2 days 25CH (CH3)CH
2-○-(C2 ratio○) 4 and C,847-○-(C2 day 4
0), 5-day 1/1/1 mixture, C9 day, 9C5 day 4
-○- (C2 ratio ○) 9-day and C, 5 ratio, 1○ (C2 is ○
) 5-day and C, 8-day 37-○- (C2 ratio 0), 2-day 0.2/1/2 mixture, (CH3)3C (CH2)8C
Day 2-0- (C2 day 40) 3-day and C, 6th day 33CH (
CH3) CH21○- (C2 day 40),. One day and C, 4
49CH (CH3) - ○ - (C2 is ○) 9-day 2/1
/1 mixture (all proportions are by weight). Particularly preferred ethoxylated nonionic surfactants {1} have at least 65% branched chain structure in their hydrocarpyl chains;
primary alcohol ethoxylates obtained from alcohols obtained by hydroformylation of random olefins and having from about 14 to about 22 carbon atoms in the hydrocarbyl chain; It is a mixture of an alcohol ethoxylate obtained from a primary alcohol having 40% branched chain structure and having 9 to 15 carbon atoms, especially 12 to 1 carbon number, and 3 to 7 moles of ethylene oxide. .

Other preferred C91C,5-ethoxylated alcohols include:
It has about 60% branched chain structure. Synthetic Anionic Surfactants Essentially anionic surfactants can be represented by the general formula below.

R3S03M where R3 is a straight-chain or branched alkyl group having 12 to 24 carbon atoms and 9 to 13 in the alkyl group.
represents a hydrocarbyl group selected from the group consisting of alkylphenyl groups having a specific carbon atom, and M represents a hydrocarbyl group selected from the group consisting of
, K, NH4 and mono-, di- and trialkanolamines having 2 to 3 carbon atoms in the alkanol group.

Preferred anionic surfactant compositions are water-soluble salts of alkylbenzene sulfonic acids, preferably alkanolamine alkylbenzene sulfonates having from about 12 to 100 carbon atoms in the alkyl group. More specifically, preferred synthetic anionic surfactants in the detergent compositions of the present invention consist of linear alkylbenzene sulfonic acid mono-, di-, or tri-ethanolamines in which the alkyl group contains on average about 12 carbon atoms.

Preferred alkalamine alkylbenzene sulfonate salts are obtained by neutralizing an alkylbenzene sulfonic acid with an alkanolamine selected from the group consisting of mono-, di-, and trietanolamines.

In this case, triethanolamine is preferred. Examples of alkanolamine salts of alkylbenzenesulfonic acids used in the present invention include triethanolamine decylbenzenesulfonate, triethanolamine dodecylbenzenesulfonate, jetanolamine undecyl besozenesulfonate, monoethanolamine tridecylbenzenesulfonate, Ethanolamine tetradecylbenzene sulfonate and mixtures thereof.

Other anionic surfactants that can be used in the present invention include organic sulfuric acid reaction products having aliphatic hydrocarbon groups containing from about 12 to about 24 carbon atoms in their molecular structure, or mixtures thereof. .

Examples of this group of synthetic detersive anionic surfactants are paraffin sulfonates, especially secondary paraffin sulfonates having about 13 to 1 needle carbon atoms, and olefin sulfonates. The anionic backsurfactant is used in the form of its sodium, potassium, ammonium salts, but preferably in the form of its mono-, di-, and trietanoamine salts, or mixtures thereof. The surfactant mixture is used in an amount of about 35% to about 75%, preferably about 40% to about 55%.

If the amount of surfactant mixture is less than about 35%, stability, phase stability, problems may occur. The upper limit is determined from the perspective of homogeneity. That is, if the surfactant mixture substantially exceeds 75%, the enzyme components will coalesce (dissolve).
It can be difficult to do so. The weight ratio of ethoxylated nonionic surfactant to synthetic anionic surfactant is usually about 1.
:1 to about 5:1, preferably about 1:1 to about 3:1. Polyacid Another essential ingredient in the composition of the present invention is a polyacid capable of forming a hydrophilic calcium collar compound.

This ranges from about 0.05% to about 1.5%, preferably about 0.05% to about 1.5%.
0.05% to about 1.0%, most preferably 0.1% to about 0.05%.
Used in an amount of 8%. The preferred type of polyacid is determined by the stability constant of its water-soluble Ca-anchor compound, and also by the enzyme stability of the detergent composition containing the polyacid and the range of 0.3% to 0.6% of citric acid as the polyacid. %, preferably 0.
This can be determined by comparison with the enzyme stability obtained by a similar composition using 5%. This stability constant defines the qualification of the polyacid, i.e. the polyacid, which is capable of sequestering calcium ions in the detergent composition, but leaves some free calcium ions in the detergent composition.

Complete sequestration of free calcium ions will result in enzyme inactivation. Here, the inactivation of the enzyme is determined by comparing the stability of the enzyme in an otherwise identical composition containing, for example, 0.3-0.6%, preferably 0.5% citric acid. It can be measured in terms of decrease in enzyme stability. A suitable water-soluble Ca-complex compound of a polyacid is
It has a logarithmic stability constant greater than about 1.5, preferably in the range of about 2.0 to 4.0.

These constants are measured at temperatures ranging from 1000 to 40°C. This stability constant is known as the "conditional stability constant" of calcium plating at a given pH. This constant is A. Written by Ringbom, "Complexion.in.
Analytical. Chemistry” (COM Yen LEXATI
ON inANALYTICALCHEMISTRY)
It can be calculated using the method of (published by Interscience). London. chemical. Society 1964 publication ``STABILI.
See also TYCONSTANTS). Suitable polyacids furthermore have stability in the compositions of the invention and 0.3% to 0.6%, preferably 0.5% in place of the polyacids.
Defined by comparison with enzyme stability of a similar composition using citric acid at the % level.

Citric acid itself is a polyacid as referred to in the present invention. It is convenient to include an appropriate amount of citric acid in a control sample during testing to select other usable polyacids. Such a control sample remains clear and homogeneous; however, in the absence of citric acid or other suitable polyacid, this control sample becomes cloudy and heterogeneous when forced to contain free calcium ions. Become. As a base liquid for quantitatively or qualitatively selecting suitable polyacids to be used in the present invention, it is possible to use: liquid detergent compositions according to the invention that do not contain polyacids; The following description is illustrative of the selection of polyacids. A liquid detergent composition is made by mixing the following ingredients.

% Trietanolamine salt of alkylbenzenesulfonic acid with an average alkyl chain length of 11.7 carbon atoms 20 Branched with 16 to 19 carbon atoms in the alkyl chain (72%
) Condensation products of fatty alcohols with 11 mol of ethylene oxide Condensation products of 20 branched (60%) fatty alcohols with 12 to 15 carbon atoms in the alkyl chain and 4 mol of ethylene oxide
10 ethanol
10 Optical Platona (Stilbene type)
0.25 triethanolamine salts of saturated fatty acids having an average of 16 to 22 carbon atoms
Approximately 1 to 2 proteolytic enzymes (commercial enzyme preparation with 15% pure enzyme content) to adjust the concentration of 0.75 triethanolamine (free) composition to 7.
0.4 Polyacid See below Moisture Residual amount up to 100% The liquid composition described above contains about 4 mmol/l of calcium composition, which mostly comes from commercial enzyme preparations;
Make adjustments if necessary.

The candidate polyacid used in the present invention and citric acid are added to each sample of the detergent composition, for example at a level of 0.5%. Addition of the candidate polyacid reduces free calcium ions in the composition through chaining. As mentioned above, the candidate polyacid has a free calcium ion content in the composition of 0.
Choose to stay within the range of 5 mmol/liter to 15 mmol/liter. For these samples, 45q
Accelerated storage tests are carried out for 40 to 6 hours at 1°C and 2 weeks at 1°C. Residual enzyme activity is analyzed using the method described below. E. Dunn and R. Brotherton, ``ANALYST'', 90, pp. 159-163 (
(1973).

A control sample containing neither boric acid nor citric acid is made. If the residual enzyme activity is of the same magnitude as that of the citric acid-containing sample and/or the control sample containing no polyacid, then the type and amount of polyacid selected is Suitable for use in compositions. C of polyacid
It will be appreciated that the a-anchor compound is water soluble, i.e. the detergent composition exhibits substantially no sediment and/or haze. The selection requires an appropriate level of free calcium in the range of 0.5 to 15 mmol. A portion of the free calcium is necessary for enzyme stability. From the minimum required enzyme level, ie 0.001%, less than 0.5 mmol of calcium ion is required. The following polyacids were tested according to the method described above.

The storage test conditions were 3 days - 2 weeks. Residual enzyme stability is calculated based on the initial activity of a given sample as 100%. This data is based on a given level of polyacid (0.5%).
It has been shown that the enzyme stability for Ca-polyacid complexes is inversely proportional to the logarithmic stability constant at the pH of the composition. Since the logarithmic stability constant is a measure of Ca ion sequestering capacity, a relatively strong chelating agent at a given pH should be included in the composition in a proportion that leaves the above-mentioned minimum level of free calcium ions in the composition. We can conclude that. Weak chelators with logarithmic stability constants of less than about 1.5 can provide enzyme stability but fail to produce homogeneous (and clear) liquid compositions.
A strong chelating agent to produce the benefits of the present invention, of course, requires a high percentage of total calcium to be present in the composition. As is clear from the above, citric acid can be effectively used to qualitatively and quantitatively select appropriate polyacid species. Besides product appearance and enzyme stability,
Preferred polyacids with logarithmic stability constants in the range of 2.0 to 4.0 are also highly resistant to bleach and builder-sensitive soils, as detailed in co-pending patent application (1). Shows excellent cleaning performance.

A broad class of preferred polyacid species for use in the compositions of the invention includes organic phosphonic acids, particularly alkylene-polyamin-polyalkylenephosphonic acids (including ethylenediaminetetramethylenephosphonic acid), hexamethylenediaminetetramethylenephosphonic acid , diethylene triamine pentamethylene phosphonic acid, and amino trimethylene phosphonic acid.

Other preferred polyacid species include: Nitrilotriacetic acid, citric acid, and diglycolic acid. A suitable polyacid can be included in the composition in the form of its acid salt or salt. Free Lucium Content The liquid detergent compositions of the present invention contain from 0.5 to 1, preferably from 1.5 to 10 mmol (skin-mol) of free calcium ions per liter of the composition.

This free calcium ion can originate from additional ingredients of the invention, especially enzyme preparations, or it can be added directly into the composition. The latter case can be carried out using any commercially available calcium salts, such as aqueous solutions of chloride and acetate. The level of free calcium ion is determined by known methods, or alternatively can be easily calculated from the logarithmic stability constant of the polyacid at the pH of the composition. Oxygen-required enzyme components are represented by alkaline proteases with isosteric points greater than 8.

The enzyme is 0.001% to about 2%, preferably about 0.0%
0.05% to about 0.8%, especially 0.02% to 0.2%. The alkaline proteases described above have isosauric points greater than about 8. Isonic points were determined by haze-phoresis on agarose. J. "Agar. Gel Electrophoresis" by Weem
R○PH○RESIS) 1965 Elsbia. It can be measured using the technique described by Publishing Company.

Regarding the value of the iso-point, "larger" means:
It relates to the absolute value of the constant dew point. The most preferred proteolytic enzyme preparations for use in the present invention are those derived from Bacillus subtilis and are derived from Novo.subtilis. “Alcalase” (AL) manufactured by Industri
CALASE) and "MAXATASE" from Gist Procades (Netherlands). These most preferred enzyme species have an isorine point of about 8.5 to about 9
．． The range is 2. pH An essential condition of the present invention is that the composition has a pH of 6.0 to 7. It is preferable to have a crucian carp in the range of about 6.0 to 7.0.

Contains the essential ingredients of the present invention, but has a pH of 6. The lower compositions present processing problems, particularly with regard to the inclusion of stilbene-type Brytona.

Compositions containing the essential ingredients of the invention but having a pH above 7.5 also fail to exhibit all of the advantages of the invention.

Liquid Carrier The liquid carrier, which is an essential component of the present invention, includes water and a liquid organic solvent.

The liquid organic carrier or solvent, which must not chemically react with any of the components of the compositions of the invention, has a carbon number of 2 to
6 and the number of hydroxyl groups is 1 to 3, selected from the group consisting of low aliphatic alcohols, ethers of diethylene glycol, and mixtures thereof. Organic cosolvents usually make up 2% to 15% of the detergent composition. Suitable examples of low aliphatic alcohols that can be used in the compositions of the invention include ethanol, n-propanol, isopropanol and butanol, 1,2-propanediol, 1,3-propanediol and n-hexanol.

Most preferred are ethanol and 1,2-propanediol. Useful examples of glycol ethers include monomethyl-, ethyl-, propyl-, and monobutyl ethers of diethylene glycol and mixtures thereof. Other organic solvents with relatively high boiling points and low vapor pressures can also be used as long as they do not react with other components.
Hydrotropes which can be used in the compositions of the invention are water-soluble alkylaryl sulfonates with an alkyl group having up to 3 carbon atoms, such as the sodium, potassium, ammonium and ethanolamine salts of xylene, toluene, ethylbenzene and isopropylbenzene sulfonic acids. It is.

These compounds are preferably used in compositions which additionally contain organic, synthetic anionic surfactants of the sulfonate type. Optional Ingredients A desirable ingredient added to the compositions of the present invention is a suitable opacifying agent.

This opacifier helps give a uniform aesthetic appearance to commercially available products. Examples of suitable opacifying agents are "LYTRON 621" and "LYTRON 607" manufactured by Monsanto Chemical Corporation.
Polystyrene, also known as Rytron opacifiers can be included in the compositions of the present invention only when polyacids are present. That is, the opacifier precipitates in compositions that do not contain polyacids. Optional ingredients include foam control agents, including brighteners, antibacterial agents, foam suppressants, and foaming agents, fragrances.

Components of this type preferably do not contain more than about 5% by weight of the composition content. One particular advantage of the compositions of the present invention is that the less water-soluble Brytona and the lightening agent can be added directly into the composition, i.e., they can be added as is, or they can be added during the formulation process. This can be added at any stage. As suds suppressants substantially hydrogenated fatty acids having 16 to 2 French carbon atoms in the hydrocarbyl chain, such as hydrogenated fish oils, and/or British Special Iso No. 57/76 (designated "Liquid There are silicone suds suppressants such as those described in "Detergent Compositions", 197 Queen Mother, Jan. 2).

In order to explain the present invention, the following examples are further shown.

Ingredient Composition (%) A B Trietanoamine salt of linear alkylbenzenesulfonic acid having an average alkyl chain length of 11.7 carbon atoms
20 20 Condensation product of a branched (72%) fatty alcohol with 16 to 19 carbon atoms in the alkyl chain and 11 moles of ethylene oxide
20 - 12~ in the alkyl chain
Condensation product of a branched (60%) fatty alcohol with 15 carbon atoms and 4 moles of ethylene oxide
10 Proteolytic enzyme (“Maxatase” 15% pure enzyme) 0.40.
Condensation product of a 1:1 mixture of 4C,4-C,5 fatty alcohol and 7 moles of ethylene oxide 30 Ethanol 10 10 Optical Brightna (stilbene type) 0.250.25 Trietanoamine (free)...1 ~2...Adjust the pH of each composition to the following.

pH: 7 pH: 6.5 9:1 mixture of dimethylpolysiloxane and airgel silica emulsified in ethoxylated fatty acids (Dow Corning: DB31) 0.1 0.2 Water
Residual amount up to 100 These liquid detergent compositions contained 4 mmol/l of calcium ions originating from the enzyme preparation.

Polyacid was added to the samples of compositions A and B as described below. After the addition of polyacid, the free calcium ion concentration decreased, but remained above 0.5 mmol liter. The test results (accelerated storage 4500: 3 songs) were as follows.

The performance of the compositions against bleach-sensitive stains was evaluated by visual inspection on a scale of 0 to 5.

On this scale 0 indicates no removal and 5 indicates complete removal. This method is fully described in the co-filed patent application {1). In relation to the above results, the performance of compositions A, 2 and B, 2 against bleach-sensitive stains is as follows:
Much better than those obtained from A3 and B3, which do not contain the combination of enzyme, polyacid and free calcium ions.

A liquid detergent composition was made by mixing the following ingredients.

Ingredients Composition A (%) Trietanoamine salt of a linear alkylbenzenesulfonic acid with an average alkyl chain length of 11.7 carbon atoms
Condensation product of 20 branched (72%) fatty alcohols with 16 to 19 carbon atoms in the alkyl chain and 11 moles of ethylene oxide
Condensation product of a branched (60%) fatty alcohol with 12 to 15 carbon atoms in the alkyl chain and 4 moles of ethylene oxide
10 ethanol
10 Optical Brightna (Stilbene type) 0.2
5 Proteolytic Enzyme (commercial enzyme preparation containing 15% pure enzyme) 9:1 mixture of 0.4 dimethylpolysiloxane and Aerogel silica emulsified in ethoxylated C,2-C,6 fatty acids
0.1 free triethanolamine 1-2 (adjusted to pH 7) water
Balanced calcium ions up to 100 liters Polyacid was added to Composition A in the following proportions.

Product appearance and residual enzyme activity were then evaluated by using the techniques set forth in the examples above. The test results were as follows. As a foam control agent, in addition to the silicone component, 0.05% of substantially hydrogenated fatty acids having 16 to 2 carbon atoms in the fatty alkyl (hydrocarbyl) chain
Similar compositions were made containing ~1%, preferably 0.2% to 0.7%.

Compositions of this type containing silicone/saturated fatty acid foam control agents exhibit the advantages of the present invention. This silicone co-foam control component is in principle up to 0.5%, preferably from 0.01% to
It is present in a proportion of 0.2%. When a pre-emulsified silicone/fatty acid foam control system is present, free calcium will not react with the fatty acids and will therefore remain in the composition! Care must be taken to avoid the formation of invisible precipitates.

The following liquid detergent composition was prepared by mixing the following components in their respective proportions. Ingredients Composition (%) Trietanoamine salt of linear alkylbenzenesulfonic acid with an average alkyl chain length of 11.7 carbon atoms
Condensation product of 20 branched* (72%) fatty alcohols with 16 to 19 carbon atoms in the alkyl chain and 11 moles of ethylene oxide
12-15 in 20 alkyl chains
Branched (60%) fatty alcohols with carbon atoms and 4
Mol of condensation product with ethylene oxide
10 proteolytic enzymes (“maxatase” 15
% pure enzyme) o
．． 4 Ethanol 10 Optical Brightener (Stilbene type) 0.25 Trietanolamine (free) 1-2 PH adjusted to 7 Dimethylpolysiloxane and Airogel silica emulsified in highly ethoxylated fatty acids (Dow Corning DE31) 9 :1 mixture 0.1 water
The residual quantity finishing detergent composition up to 100 contains 4 mmol of calcium ions originating from the proteolytic enzyme formulation.

After addition of the polyacid, more than 0.5 mmol of free calcium ions remain per liter of composition. Polyacid was added at various levels as shown in the table below.

Residual enzyme activity and product appearance after 3 pongee cycles at 44°C are as follows:
It was as follows.

A liquid detergent composition of the present invention was made by mixing the following ingredients.

Component Composition (%) Linear alkylbenzenesulfonic acid (average alkyl chain length 1
1.7 carbon atoms) 13.7 Triethanolamine 8.5 Branched with 16 to 19 carbon atoms in the alkyl chain (72
%) Condensation product of a fatty alcohol with 11 mol of ethylene oxide 20.0 Condensation product of a branched (60%) fatty alcohol with 12 to 15 carbon atoms in the alkyl chain and 4 mol of ethylene oxide
10.0 proteolytic enzyme (contains 1.5 Anson units/ta of "Maxatase")
1.0 ethanol
10・〇C, 8-C24 saturated fatty acid
9:1 mixture of airgel silica emulsified in 0.5 dimethylpolyloxane and ethoxylated fatty acids○-1
See below polyacid
Minor components including water, pH 7 modifier and Brytona, see below, balance up to 100% The compositions of the present invention were worked up by adding the amounts of polyacid shown in the table below and also adjusting the total amount of lucium.

The free calcium ion content after addition of the polyacid is between 0.5 mmol/liter and 15 mmol/liter. Although the compositions (c to f) of the present invention did not show any precipitates,
Prior art compositions were found to be hazy.

Claims (1)

[Scope of Claims] 1. An enzyme-containing detergent composition characterized by containing the following (a) to (e). (a) A surfactant mixture of (i) and (ii) below at about 35% to about 75% (by weight) of the composition. (i) an ethoxylated nonionic surfactant selected from the group consisting of ethoxylated aliphatic alcohols: ethoxylated alkylphenols and mixtures thereof;
i) Synthetic anionic surfactants selected from the group consisting of compounds of the general formula R_3SO_3M. However, in this formula, R_3 is a straight chain or branched alkyl group having 12 to 24 carbon atoms and an alkyl group having 9 to 1 carbon atoms.
5 represents a hydrocarpyl group selected from the group consisting of alkylphenyl groups, M represents sodium, potassium, ammonium, and mono-, di-, and tri-alkanolamines (however, the alkanol group has 2 to 3 carbon atoms). A salt-forming cation selected from the group consisting of: Also, the weight ratio of ethoxylated nonionic surfactant to synthetic anionic surfactant is from about 1:1 to about 5:1. (b
) from about 0.05% to about 1.5% (by weight) of a polyacid selected from the group consisting of ethylenediaminetetramethylenephosphonic acid, hexamethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and aminotrimethylenephosphonic acid; (c) from 0.5 mmol to 15 mmol per liter of the composition;
Free calcium ions, (d) 0.001% to about 2%
(by weight) of an alkaline proteolytic enzyme having an isoelectric point greater than about 8, and (e) the remaining amount of the composition, a liquid. This liquid is water and a liquid organic solvent, and this liquid organic solvent is a lower aliphatic alcohol having 2 to 6 carbon atoms and 1 to 3 hydroxyl groups, and a mixture thereof. In addition, the liquid organic solvent is about 2% to about 15% (by weight) of the total composition,
The pH of this composition is about 6.0 to about 7.5. 2. The surfactant mixture is present in an amount of about 40% to about 55% (by weight) and the weight ratio of ethoxylated surfactant to synthetic anionic surfactant is about 1:1 to about 3:1. , the composition according to claim 1. 3. A composition according to claim 1, wherein the free calcium ions are present in an amount of 1.5 mmol to 10 mmol per liter. 4. The composition of claim 3, wherein the proteolytic enzyme is present in an amount from 0.005% to about 0.8% (by weight). 5 The nonionic surfactant has a hydrocarbyl group of about 4 to 1 mole of primary aliphatic alcohol having about 12 to about 20 carbon atoms.
The anionic surfactant is selected from the group consisting of ethoxylated primary aliphatic alcohols to which about 14 moles of ethylene oxide are attached and mixtures thereof, and the anionic surfactant is a mono- or di-alkyl benzene sulfonic acid having an alkyl group of about 12 to about 15 carbon atoms. and tri-alkanolamine salts and mixtures thereof. 6. The composition according to claim 5, further comprising a foam control agent consisting of the following (a) and (b). (a) 0.01% to 0.2% (by weight) silicone;
(b) 0.05% to 1% (by weight) of saturated fatty acids having from about 16 to about 24 fatty alkyl chain carbon atoms.